Electrocarboxylation organic halide

Co(TPP) has been demonstrated to act as a catalyst for the electrocarboxylation of benzyl chloride and butyl bromide with CO - to give PhCHiCfOiOCH Ph and Bu0C(0)C(0)0Bu, respectively. The propo.sed mechanism involved Co(TPP)R and [Co(TPP-N-R) as intermediates (the latter detected by spectroscopy) in the catalytic production of free R or R-, which then reacted directly with Co(TPP) precipitated on graphite foil has been successfully used for the determination of organic halides, including DDT and 1,2,3,4,5,6-hexachlorocyclohexane (lindane), to sub-ppm level in aqueous solution. Deoxygenation of the solutions is not required, and the technique is moderately insensitive to the ionic composition of the solution. ... 

The catalyst is not necessary either for the electrocarboxylation of aryl halides or various benzylic compounds when conducted in undivided cells and in the presence of a sacrificial anode of aluminum [105] or magnesium [8,106], Nevertheless both methods, i.e., catalysis and sacrificial anode, can be eventually associated in order to perform the electrocarboxylation of organic halides having functional groups which are not compatible with a direct electroreductive process. 

The electrocarboxylation of organic halides ideally involves the following reaction scheme [21] ... 

Our synthetic method for CO2 fixation was based on the use of transition-metal catalysis combined with electrochemical techniques [10]. Within this methodology, the electrochemical CO2 fixation into some alkenes has been reported to afford carbo lic acids in a reductive hydrocarboxylation-tjqje reaction catalyzed by nickel complexes, under mild conditions [11]. The electrocarboxylation of organic halides to the corresponding carboxylic acids has also been reported [12], yields and efficiency of the reaction being strongly dependent on the reaction conditions. 

Electroassisted Barbier Reactions 1985 and 1986. More recently a new and efficient method was reported for the electrocarboxylation of organic halides, using an undivided electrolytic cell and a sacrificial magnesium electrode [101]. 

---